Ziegler-Natta polymerization technology provides opportunities for the production of polyolefins with controlled stereo-regularity and molecular weight. However, due to the lack of appropriate functionality, the polyolefin polymers produced by this technology can be deficient in terms of poor adhesive properties, low affinity for dyes, poor permeability, and low compatibility with more polar polymers, fillers-reinforcing or not- and substrates. The incorporation of functional groups in a hydrocarbon based polymer can dramatically change the chemical and physical properties of the polymer. Unfortunately, current generation Ziegler-Natta catalysts are generally incompatible with polar co-monomers because of catalyst poisoning. Despite various efforts, including using borane co-monomer and monomers with protected polar functionalities, the search for more efficient reaction routes to produce functionalized polyolefins via a coordination polymerization process continues.
The efficient copolymerization of vinylsilanes with α-olefins where silyl-functionalized polyolefins would be generated represents a possible approach to this long-standing problem. Although the copolymerization of α-olefins with allysilanes using Ziegler-Natta type of catalysts has been reported, its copolymerization with bulky and readily available functional vinylsilanes has been very difficult to achieve. Silyl-functionalized polyolefins would not only offer novel physical and chemical properties, but could also be used as a precursor for making other functionalized polyolefins because the silyl group is easily modified and can be used to further crosslink the polyolefin.
JP 2008-177912 discloses copolymerization of a specific alkenyl silane ingredient [D] to two or more alpha olefin under metallocene system polymerization catalyst. The alkenyl silane (D) has the structure (IV) shown below

(R2 is hydrogen, halogen, or a hydrocarbon group of the carbon numbers 1-4 among formula (IV), and three R2 may be the same or may differ.) R8 and R9 may be the same, or may differ from each other, and are hydrogen or a hydrocarbon group of the carbon numbers 1-4. m is 0 or 1. Paragraph [087] mentions as examples: allyltrimethylsilane, vinyltrimethylsilane, an allyltriethylsilane, vinyltriethylsilane. However, copolymerization with vinyltrimethylsilane results in poor co-monomer incorporation rate as will be shown in the examples.
U.S. Pat. No. 4,413,066 discloses crosslinkable polyethylene resin composition comprising a unit of ethylene and a unit of an ethylenically unsaturated silane compound obtained under high pressure conditions using an autoclave.
U.S. Pat. No. 4,397,981 discloses copolymerization of ethylene and an unsaturated silane compound, most preferred being vinyltrimethoxysilane, vinyltriethoxysilane and gamma-methacryloxypropyltrimethoxysilane, under autoclave.
U.S. Pat. No. 3,225,018 discloses copolymerizing ethylene and a vinyltrialkoxysilane in contact with a free radical catalyst at high pressure.
U.S. Pat. No. 4,446,283 discloses a copolymer consisting essentially of ethylene and an unsaturated silane compound represented by the formula CH2═C(R)COO(CH2)xSiR′y(OCH3)3-y wherein R is hydrogen or a C1 to C4 alkyl group, R′ is a C1 to C4 alkyl group, x stands for an integer from 1 to 6, a and y stands for 0, 1 or 2. The copolymer is also obtained under high pressure conditions typically in autoclave.
EP 1 849 816 discloses silane group containing polyolefin which has been obtained by copolymerisation. In the case of polyolefins, preferably polyethylene, the copolymerisation is preferably carried out with an unsaturated silane compound represented by the formula
R1SiR2qY3-q (II) wherein R1 is an ethylenically unsaturated hydrocarbyl, hydrocarbyloxy or (meth)acryloxy hydrocarbyl group, R2 is an aliphatic saturated hydrocarbyl group, Y which may be the same or different, is a hydrolysable organic group and q is 0, 1 or 2. The most preferred compounds are vinyl trimethoxysilane, vinyl bismethoxyethoxysilane, vinyl triethoxysilane, gamma_(meth)acryloxypropyltrimethoxysilane, gamma(meth)acryloxypropyltriethoxysilane, and vinyl triacetoxysilane.